oxoacids of h alogen s; diversification in chemistry of these elements.

• en u m er at e t h e u ses of n obl e Having lear nt the chemistr y of elements of Gr ou ps

gases; 13 and 14 of the p-block of per iodic table in Class XI,

b
• appr eci at e t h e i m por t an ce of you wi l l l ear n t h e ch em i st r y of t h e el em en t s of
t h ese el em en t s an d of the
t h ei r apatite
su bsequ family,
ent grCa (POin
ou9ps 4 )6 .this
CaXUnit.
2 (X = F, Cl or OH) (e.g., flu orapatite
com pou n ds in ou r day to dayCa 9 (PO 4 )6 . CaF 2 ) which ar e the m ain com ponents of phosphate r ock s.
life.

o
Phosphor u s is an essential constitu ent of anim al and plant m atter. It
7.1 Group 15 is present
Gr ou p 15 in bones
in clu des as ,well
n it r ogen phas in or
osph living
u s, cells.
ar senPhosphoproteins
ic, an t imon y an are
d present
in m ilk and eggs. Ar senic, antim ony and bism u th ar e fou
bismu th. As we go down the gr ou p, ther e is a shift fr om non-metallic ainly asnd m

tt
Elements su lphide
to metallic

along
typical metal.
m iner
thr ou gh
The important
ar e non-metals,
als.
metalloidic
ar senic and
with their
atomic
electr
char acter. Nitr ogen and phosphor u s
and physical
antimony
onic
properties
metalloids
configu r ations ar
and of
e
this th
bismu
given in
grou
isp aelements
Table 7.1.
no
7.1.1 Occur r en ce Tabl e 7 .1lar
Molecu : Atnitr
om ogen
i c an dcompr
Ph y siises
cal Pr
78%operby
t i esvolu
of me
Gr ouof
p 1the
5 Elatmospher
em en t s e.

e
In the ear th’s cr u st, it occu r s as sodiu m nitr ate, NaNO3 (called Ch ile
Pr op er saltpetr
ty N
e) and potassiu m nitrPate (IndianAs
saltpetr e). ItSb Bi
is fou nd in the
form of proteins in plants and animals. Phosphoru s occu rs in minerals

h
At om ic n u m ber 7 15 33 51 83
–1
At om ic m ass/ g m ol 14.01 30.97 74.92 121.75 208.98

T lis
2 3 2 3 10 2 3 10 2 3 14 10 2 3
Electronic configuration [He]2s 2p [Ne]3s 3p [Ar]3d 4s 4p [Kr]4d 5s 5p [Xe]4f 5d 6s 6p
Ion isat ion en t h alpy I 1402 1012 947 834 703
–1

R
(∆iH/ (k J m ol ) II 2856 1903 1798 1595 1610

b
III 4577 2910 2736 2443 2466
El ect r on egat i vi t y 3.0 2.1 2.0 1.9 1.9

E u
a
Covalen t r adiu s/ pm 70 110 121 141 148
b b b c c
Ion ic r adiu s/ pm 171 212 222 76 103

C ep
M elt in g poin t / K 63* 317 d 1089 e 904 544
d f
Boilin g poin t / K 77.2* 554 888 1860 1837
–3 g h
Den sit y/ [g cm (298 K)] 0.879 1.823 5.778 6.697 9.808

g
III

N r
E single bond (E = element); E ; E ;
h
b

At 63 K; Grey α-form; * Molecular N2 .

3– c 3+ d
White phosphorus;
e f
Grey α-form at 38.6 atm; Sublimation temperature;

© be
Tr ends of som e of the atom ic, physical and chem ical pr oper ties of the
gr ou p ar e discu ssed below.

7.1.2 El ect r on i c The valence shell electr onic configu r ation of these elem ents is ns 2 np 3 .
Configurat ion The s or bit al in t h ese elem en ts is com plet ely filled and p or bit als ar e
half-filled, m ak ing their electr onic configu r ation extr a stable.

to
7.1.3 At om i c an d
I on i c Radi i
Coval en t an d i on i c (i n a par t i cu l ar st at e) r adi i i n cr ease i n si ze
down t h e gr ou p. Th er e is a con sider able in cr ease in covalen t r adiu s
fr om N t o P. H owever , fr om As t o B i on l y a sm al l i n cr ease i n

t
coval en t r ad i u s i s ob ser ved . Th i s i s d u e t o t h e p r esen ce of
com pl et el y fi l l ed d an d / or f or bi t al s i n h eavi er m em b er s.

o
7.1.4 I on i sat i on Ionisation enthalpy decr eases down the gr ou p du e to gr adu al incr ease
En t h al py in atomic size. Becau se of the extra stable half-filled p orbitals electronic

n
configu r ation and sm aller size, the ionisation enthalpy of the gr ou p 15
elem ents is m u ch gr eater than that of gr ou p 14 elem ents in the
cor r esponding per iods. The or der of su ccessive ionisation enthalpies,
as expected is ∆i H 1 < ∆i H 2 < ∆i H 3 (Table 7.1).

Ch em i st r y 166
 Pr oper t i es while all others are solids. Metallic character increases down the group.
Nitrogen and phosphorus are non-metals, arsenic and antimony metalloids
and bismuth is a metal. This is due to decrease in ionisation enthalpy and
increase in atomic size. The boiling points, in general, increase from top to
bottom in the group but the melting point increases upto arsenic and then
decreases upto bismuth. Except nitrogen, all the elements show allotropy.
7.1.7 Ch em i cal
Pr oper t i es
Ox i d a t i on st a t es a n d t r en d s i n ch em i ca l r ea ct i vi t y
The common oxidation states of these elements are –3, +3 and +5.
The tendency to exhibit –3 oxidation state decreases down the group due

he
T li s
to increase in size and metallic character . In fact last member of the gr oup,
bismuth hardly forms any compound in –3 oxidation state. The stability
of +5 oxidation state decreases down the group. The only well characterised
Bi (V) compound is BiF 5. The stability of +5 oxidation state decreases and

R
that of +3 state increases (due to inert pair effect) down the group. Nitrogen

E u b
exhibits + 1, + 2, + 4 oxidation states also when it reacts with oxygen.
Phosphorus also shows +1 and +4 oxidation states in some oxoacids.
In the case of nitr ogen, all oxidation states fr om +1 to +4 tend to
dispr opor tionate in acid solu tion. For exam ple,

C ep
3HNO2 → HNO 3 + H 2 O + 2NO
Sim ilar ly, in case of phosphor u s near ly all inter m ediate oxidation
states disproportionate into +5 and –3 both in alk ali and acid. However

N r
+3 oxidation state in case of ar senic, antim ony and bism u th becom es
incr easingly stable with r espect to dispr opor tionation.
Nitr ogen is r estr icted to a m axim u m covalency of 4 since only fou r

© be
(one s and three p) orbitals are available for bonding. The heavier elements
have vacant d or bit als in t h e ou t er m ost sh ell wh ich can be u sed for
–
bonding (covalency) and hence, expand their covalence as in PF 6.
An om a l ou s p r op er t i es of n i t r ogen
Nit r ogen differ s fr om t h e r est of t h e m em ber s of t h is gr ou p du e t o
it s sm all size, h igh elect r on egat ivit y, h igh ion isat ion en t h alpy an d
n on -availabilit y of d or bi t al s. Nit r ogen h as u n i qu e abil it y t o for m

t o
p π-p π m u l t i p l e bon ds wi t h i t sel f an d wi t h ot h er elem en t s h avi n g
sm all size an d h igh elect r on egat ivit y (e.g., C, O). Heavier elem en t s of
t h is gr ou p do n ot for m pπ-pπ bon ds as t h ei r at om ic or bit al s ar e so

t
l ar ge an d di ffu se t h at t h ey can n ot h ave effect i ve over l appi n g.
Th u s, n it r ogen exist s as a diat om ic m olecu le wit h a t r iple bon d (on e
s and two p) between the two atom s. Consequ ently, its bond enthalpy

n o (941.4 k J m ol –1 ) is ver y h igh . On t h e con t r ar y, ph osph or u s, ar sen ic

an d an t im on y for m sin gle bon ds as P–P, As–As an d Sb–Sb wh ile
bism u t h for m s m et allic bon ds in elem en t al st at e. However , t h e sin gle
N–N bon d is weak er t h an t h e sin gle P–P bon d becau se of h igh
in t er elect r on ic r epu lsion of t h e n on -bon din g elect r on s, owin g t o t h e
sm all bon d len gt h . As a r esu lt t h e cat en at ion t en den cy is we ak er in

n it r ogen . An ot h er fact or wh ich affect s t h e ch em ist r y of n it r ogen 167 isTh e p-Block Elem en t s
t h e absen ce of d or bit als i n i t s valen ce sh el l. Besides r est r ict in g i t s
covalen cy t o fou r , n it r ogen can n ot for m d π –p π bon d as t h e h eavier
elem ents can e.g., R 3 P = O or R3 P = CH 2 (R = alk yl gr ou p). Phosphor u s
an d ar sen ic can for m d π –d π bon d also wit h t r an sit ion m et als wh en
t h eir com pou n ds lik e P(C 2 H 5 )3 an d As(C 6 H 5 )3 act as li gan ds.
(i) Reactivity tow ards hy drogen : All t h e elem en t s of Gr ou p 15
for m h ydr ides of t h e t ype EH 3 wh er e E = N, P, As, Sb or Bi.

d
Som e of t h e pr oper t ies of t h ese h ydr ides ar e sh own in Table
7.2. Th e h ydr ides sh ow r egu lar gr adat ion in t h eir pr oper t ies.

e
Th e st abilit y of h ydr ides decr eases fr om NH 3 t o BiH 3 wh ich can
b e ob ser ved fr om t h ei r b on d d i ssoci at i on en t h al p y.
Con sequ en t ly, t h e r edu cin g ch ar act er of t h e h ydr ides in cr eases.

Pr op er t y NH 3 PH 3T ish
Am m on ia is on ly a m ild r edu cin g agen t wh ile BiH 3 i s t h e
st r on gest r edu cin g agen t am on gst all t h e h ydr ides. Basicit y also
decr eases in t h e or der NH 3 > PH 3 > AsH 3 > SbH 3 > BiH 3 .
Tabl e 7 .2 : Pr oper t i es of Hy dr i des of Gr ou p 1 5 El em en t s

AsH 3 SbH 3 Bi H 3
 bl
Usess: The m ajor u se of nitr ic acid is in the m anu factu r e of am m oniu m nitr ate
for fer tiliser s and other nitr ates for u se in explosives and pyr otechnics. It is

E u
also u sed for the preparation of nitroglycerin, trinitrotolu ene and other organic
nitr o com pou nds. Other m ajor u ses ar e in the pickling of stainless steel ,
etching of m etals and as an oxidiser in r ock et fu els.

7.6 Phosphorus —
A llotropic
C ep Phosphor u s is fou nd in m any allotr opic for m s, the im por tant ones
being white, r ed and black .
Forms

N r Whi t e phosphor us is a translucent white waxy solid. It is poisonous,

insolu ble in water bu t solu ble in car bon disu lphide and glows in dar k
(chem ilu m inescence). It dissolves in boiling NaOH solu tion in an iner t

© be
atm ospher e giving PH 3.

P4 + 3NaOH + 3H 2 O → PH 3 + 3NaH 2 PO2

( sodiu m hypophosphit e)
P White phosphor u s is less stable and ther efor e, m or e r eactive than
the other solid phases u nder nor m al conditions becau se of angu lar
60°
str ain in th e P4 m olecu le wh er e t h e an gles ar e on ly 60°. It r eadily
P

to P catches fir e in air to give dense white fu m es of P4 O10 .

P4 + 5O2 → P4 O10

t
It consists of discr ete tetr ahedr al P 4 m olecu le as shown in Fig. 7.2.
Fi g. 7 .2
White phosphorus
Red ph osph or us is obtained by heating white phosphor u s at 573K

o
in an inert atmosphere for several days. When red phosphorus is heated
u nder high pressu re, a series of phases of black phosphoru s is formed.
Red phosphor u s possesses ir on gr ey lu str e. It is odou r less, non-

n
poisonou s and insolu ble in water as well as in car bon disu lphide.
Ch em i cal l y, r ed ph osph or u s i s m u ch l ess r eact i ve t h an wh i t e
phosphor u s. It does not glow in the dar k .

175 Th e p-Block Elem en t s

P P P It i s pol ym er i c, con si st i n g of ch ai n s of P4
tetr ahedr a link ed together in the manner as shown
in Fig. 7.3.
P P P P P P
Bl ac k p h osp h or u s h as t wo for m s α-bl ack
ph osph or u s an d β-bl ack ph osph or u s. α-Bl ack
P P P
ph osph or u s is for m ed wh en r ed ph osph or u s is
Fi g.7 .3 : Red phosphorus heated in a sealed tu be at 803K. It can be su blimed
in air and has opaqu e m onoclinic or r hom bohedr al

d
cr ystals. It does not oxidise in air. β-Black phosphor u s is pr epar ed by
heating white phosphor u s at 473 K u nder high pr essu r e. It does not

e
bu r n in air u pto 673 K.
7.7 Phosphine Pr ep a r a t i on

T lish
Phosphine is prepared by the reaction of calciu m phosphide with water
or dilu te HCl.
Ca3 P2 + 6H 2O → 3Ca(OH)2 + 2PH 3
Ca3 P2 + 6HCl → 3CaCl 2 + 2PH 3

R
In the labor ator y, it is pr epar ed by heating white phosphor u s with

b
concentr ated NaOH solu tion in an iner t atm ospher e of CO2 .
P4 + 3NaOH + 3H 2 O → PH 3 + 3NaH 2 PO 2

E u ( sodiu m h ypophosphite)
When pu r e, it is non inflammable bu t becomes inflammable owing

C ep
to the pr esence of P2 H 4 or P4 vapou r s. To pu r ify it fr om the impu r ities,
it is absorbed in HI to form phosphonium iodide (PH 4 I) which on treating
with KOH gives off phosphine.

N r
PH 4 I KOH

Pr op er t i es
KI H 2 O PH 3

It is a colou r less gas with r otten fish sm ell and is highly poisonou s.
It explodes in contact with traces of oxidising agents lik e HNO 3 , Cl 2 and
 _
@unacademyplusdiscounts
10.35 General Properties and Structures of the Elements 449

Phosphorus
Phosphorus is solid at room temperature. White phosphorus is soft, waxy and reactive. I t reacts with moist
air and gives out light (chemiluminescence). I t ignites spontaneously in air at about 35 °C, and is stored
under water to prevent this. I t is highly toxic. I t exists as tetrahedral P4 molecules, and the tetrahedral
structure remains in the liquid and gaseous states. A bove 800 °C P4 molecules in the gas begin to dissociate
into P2 molecules, which have a bond energy of 489.6 kJ mol -1. (This is only half the value for N 2 because
the orbitals in the third shell are much larger and give relatively poor pp–pp overlap.) I f white phosphorus
is heated to about 250 °C, or a lower temperature in the presence of sunlight, then red phosphorus is
formed. This is a polymeric solid, which is much less reactive than white phosphorus. I t is stable in air and
does not ignite unless it is heated to 400 °C. I t need not be stored under water. I t is insoluble inorganic
solvents. H eating white phosphorus under high pressure results in a highly polymerized form of P called
black phosphorus. This is thermodynamically the most stable allotrope. I t is inert and has a layer structure
(Figure 10.28). Other more doubtful allotr opes have been reported.

Figure 10.28 The structure of black phosphorus. The atoms are

arranged in corrugated planes in crystalline black phosphorus
(Van Wazer, J.R., Phosphorus and Its Compounds, Vol.1, Interscience,
New York – London, 1958, p.121).

Bond t ype
The majority of compounds formed by this gr oup are covalent.

s p
Outer electronic structure
of group 15 element

three unpaired electrons form bonds with s bond other atoms

four electron pairs give a tetrahedral shape with one position
occupied by a lone pair

Table 10.16 Radii, ionization energies and electronegativity

Covalent Ionization energies Pauling’s
radius (Å) (kJ mol- 1) electronegativity
1st 2nd 3rd
N 0.74 1403 2857 4578 3.0
P 1.10 1012 1897 2910 2.1
As 1.21 947 1950 2732 2.0
Sb 1.41 834 1590 2440 1.9
Bi 1.52 703 1610 2467 1.9

Chapter-10.indd 449 2/27/2018

 _
n it r ogen . An ot h er fact or wh ich affect s t h e ch em ist r y of n it r ogen is
@unacademyplusdiscounts
t h e absen ce of d or bi t al s i n i t s valen ce sh ell. B esides r est r i ct in g i t s
covalen cy t o fou r , n it r ogen can n ot for m d π –p π bon d as t h e h eavier
elem ents can e.g., R 3 P = O or R3P = CH 2 (R = alk yl gr ou p). Phosphor u s10.36 Hydrides 451
an d ar sen ic can for m d π –d π bon d also wit h t r an sit ion m et als wh en
t h eir | com
10.36 pou n ds lik e P(C 2 H 5 )3 an d As(C 6 H 5 )3 act as l i gan ds.
HYDRIDES
(i) Reactivity tow ards hy drogen : All t h e elem en t s of Gr ou p 15
for mallhform
The elements ydr ides of hydrides
volatile t h e t ype EH 3 whMerHe3, which
of formula E = N, areP,
all As, Sb orfoul
poisonous, Bi.smelling gases. On
descending Som

d
theegroup
of t hfrom
e prNHoper3 tot ies
BiH of
3: t h ese h ydr ides ar e sh
7.2. Th e h ydr ides sh ow r egu lar gr adat ion in t h eir pr oper t ies.
1. The hydrides become increasingly dif cult to prepare.

e
Th e st abilit y of h ydr ides decr eases fr om NH 3 t o BiH 3 wh ich can
2. Theirbstability
3. TheirCon
e ob ser
reducing
decreases.
sequ power
ved fr om t h ei r b on d d i ssoci at i on en t h al p y.
en t ly,increases.
own in

t h e r edu cin g ch ar act er of t h e h ydr ides in cr eases.

Table

Am
st

T lishr
m
on
on ia
gest r
is
4. The ease of replacing thely
edu
on
cin g
a m ild
hydrogen
agen t
atoms
am
r edu
on
by cin
gst all
g gragen
other
t h
oupst such
e h ydr
whasileCl BiH
ides.
or M3ei decr
Basicit y
s t heases.
also
e
5. Their ability to act as electron donors, using the lone pair of electrons for coordinate bond formation,
decr eases in t h e or der NH 3 > PH 3 > AsH 3 > SbH 3 > Bi H 3 .
decreases.
Tabl e 7 .2 : Pr oper t i es of H y dr i des of Gr ou p 1 5 El em en t s

R
AmmoniaPrNH 3 ty
op er NH 3 PH 3 AsH 3 SbH 3 Bi H 3

b
NH 3 is a colourless gas with a pungent odour. The gas is quite poisonous. I t dissolves very readily in water
M eltevolution
with the in g poinoft / heat.
K A t 20195.2
°C and one139.5
atmosphere 156.7 –
185g NH dissolves
pressure 53.1 in 100 g water. This

E u
3
corresponds to 702 volumes
Boilin g poin t / K of NH dissolving
238.5
3 in
185.5 1 volume of H O. I
210.6 2 254.6n solution ammonia
290 forms ammonium
hydroxide NH 4OH , and behaves as a weak base.
(E–H) Dist an ce/ pm 101.7 141.9 151.9 170.7 –
NH 4+ + OH - K = 1.8 × 105 mol l -1

C ep
NH 3 + H 2O
NH 3 HEH
and NH an gle (°) 107.8 93.6 91.8 91.3 –
4OH both react with acids, forming ammonium salts. These salts resemble potassium salts
in solubility and in their crystal structures. Like the Group 1 salts, ammonium salts are typically colourless.
∆ H V / k J m ol –1 –46.1 13.4 66.4 145.1 278

N r
There fare some differences. A mmonium salts are usually slightly acidic if they have been formed with
strong acids such askHJ NO –1
∆diss H V (E–H)/ 3, H Cl and
m ol 389H 2SO 4, 322
since NH 4OH is only a weak
297 255 base. A mmonium
– salts decompose
quite readily on heating. I f the anion is not particularly oxidizing (e.g. Cl - , CO 2- 3 or SO 2-
4 ) then ammonia
is evolved:

© be
(ii) Reactivity tow ards oxy gen NH:4Cl All theat
h eseNH
elem
3 + en t s for m t wo t ypes
H Cl
of oxides: E 2 O 3 an d E(NH 2 O5 . ) Th e oxide
heat in t h e h igh er oxidat ion st at e
4 2SO 4 2NH 3 + H 2SO 4
of t h e elem en t is m or e acidic t h an t h at of lower oxidat ion st at e.
This
I f the anion eirmore
acidic ch ar (e.g.
oxidizing act erNO decr
- eases - down- t h e2-gr ou p. Th+ e oxides of
2 , NO 3 , ClO 4 , Cr O 7 then NH 4 is oxidized to N 2 or N 2O.
t h e t ype E 2 O 3 of n it r ogen an d ph osph 2or u s ar e pu r ely acidic,
t h at of ar sen ic an d an t-imI I I on
+I Iy
I am ph ot er0ic an d t h ose of bism u t h
pr edom in an t ly basic. NH 4 NO 2 ¾¾¾ ® N 2 + 2H 2O
heat

to (iii) Reactivity tow ards halogens: Th ese elem en t s r eact t o for m t wo

ser i es of h al i d es: E X
- I I I +V
NH 3 an d Eheat
4 NO 3 ¾ ¾¾
X 5®
+I
. Ni
N 2tO
pentahalide du e to non-availability of the d or bitals in its valence
r ogen
+ 2H 2Od oes n ot for m

t
sh ell. Pen t ah alides ar e) Cr m or e covalen ® N 2t +t h4HanOt +r ih
Cralides. All t h e
2O 7 ¾ ¾¾
heat
(NH 4 2 2 2O 3
t r ih alides of t h ese elem en t s except t h ose of n it r ogen ar e st able.
In case of n it r ogen , on ly NF 3 i s k n own t o be st able. Tr ih alides

o NH 3 burns

The samesu
except

ch as,
reaction
BiF 3 with
in dioxygen ar eapr

Ca 3in
occurs N 2air,
edom
pale

(cal
yellow

butcithe
i n aname:

u mheat
t ly covalen t in n at u r e.
(iv) Reactivity tow ards metals : All t h ese elem en t s r eact wit h m et als
4NH + 3O
t o for m t h eir bin ar y com pou3 n ds 2exh ibit
n itofr ireaction
de) Cais
2N 2 + 3H 2O
in g –3 oxidat ion st at e,
3 Pinsuf
2 (calciu
cientmto maintain
is supplied, for example in a gas ame. Certain mixtures of NH /O and NH /air are explosive.
ph osph ide),
combustion unless heat
 C epu Intext Q uestion
7.3 Why is N2 less r eact ive at r oom t em per at u r e?

7.3 Ammonia
N r Pr ep a r a t i on

© be
Am m onia is pr esent in sm all qu antities in air and soil wher e it is
for m ed by the decay of nitr ogenou s or ganic m atter e.g., u r ea.
NH 2 CONH 2 + 2H 2 O → ( NH 4 )2 CO 3 ⇌ 2NH 3 + H 2 O + CO 2

On a small scale ammonia is obtained from ammoniu m salts which

decom pose when tr eated with cau stic soda or calciu m hydr oxide.
2NH 4 Cl + Ca(OH)2 → 2NH 3 + 2H 2O + CaCl 2

to (NH 4 )2 SO 4 + 2NaOH → 2NH 3 + 2H 2 O + Na2 SO 4

On a lar ge scale, am m onia is m anu factu r ed by Haber ’s pr ocess.

t
N2 (g) + 3H 2 (g) Ö 2NH 3 (g); ∆f H 0 = – 46.1 k J m ol –1
In accor dance with Le Chatelier ’s pr inciple, high pr essu r e wou ld

o
favou r the for m ation of am m onia. The optim u m conditions for the
pr odu ction of am m onia ar e a pr essu r e of 200 × 10 5 Pa (abou t 200

n
atm ), a tem per atu r e of ~ 700 K and the u se of a catalyst su ch as ir on
oxide with sm all am ou nts of K 2 O and Al 2 O3 t o in cr ease t h e r at e of
attainment of equilibrium. The flow chart for the production of ammonia
is sh own in Fig. 7.1. Ear lier, ir on was u sed as a cat alyst wit h
m olybdenu m as a pr om oter.
Ch em i st r y 170
 e
Fi g. 7 .1
Flow chart for the
manufacture of

h
ammonia

pu T
Pr op er t i es

is
Am m onia is a colou r less gas with a pu ngent odou r. Its fr eezing and
boiling points ar e 198.4 and 239.7 K r espectively. In the solid and
re R liqu id states, it is associated thr ou gh hydr ogen bonds as in the case

bl
N
of water and that accou nts for its higher m elting and boiling points
H H than expected on the basis of its molecular mass. The ammonia molecule
E
H is tr igonal pyr am idal with the nitr ogen atom at the apex. It has thr ee
bond pair s and one lone pair of electr ons as shown in the str u ctu r e.
Am m onia gas is highly solu ble in water. Its aqu eou s solu tion is
be C

weak ly basic du e to the for m ation of OH – ions.

NH 3(g) + H 2 O(l) l NH 4 + (aq) + OH – (aq)
o N

It forms ammoniu m salts with acids, e.g., NH 4 Cl, (NH 4 )2 SO 4, etc. As

a weak base, it pr ecipitates the hydr oxides (hydr ated oxides in case of
som e m etals) of m any m etals fr om their salt solu tions. For exam ple,
Zn SO 4 ( aq ) + 2NH 4 OH ( aq ) → Zn ( OH )2 ( s ) + ( NH 4 )2 SO 4 ( aq )
tt ©

( wh ite ppt )
FeCl 3 aq NH 4 OH aq Fe2 O 3 .x H 2 O s NH 4 Cl aq
br own ppt
Th e pr esen ce of a lon e pair of elect r on s on t h e n it r ogen at om of
t h e am m on ia m olecu le m ak es it a Lewis base. It don at es t h e elect r on
pair an d for m s lin k age wit h m et al ion s an d t h e for m at ion of su ch
com plex com pou n ds fin ds applicat ion s in det ect ion of m et al ion s
2+ +
su ch as Cu , Ag :
2+ 2+
Cu (aq) + 4 NH 3 (aq) Ö [Cu (NH 3)4 ] (aq)
(blu e) (deep blu e)
−
+
( aq ) + Cl ( aq ) → AgCl ( s )
no

Ag
(colou r less) (wh it e ppt )
AgCl ( s ) + 2NH 3 ( aq ) → Ag ( NH 3 )2 Cl ( aq )
(wh it e ppt ) (colou r less)

171 Th e p-Block Elem en t s

 3 2 2 4 2 3
454 Chapt er 10 The p-Block Elements and their Compounds
(NH 4) 2CO 3 + CaSO 4 CaCO 3 + (NH 4) 2SO 4
The
Smallhydrides
amounts PHof3, diammonium
A sH 3 and SbHhydrogen
3 would be expected(NH
phosphate to be similar. H owever, the bond pairs of electrons
4) 2H PO 4 and ammonium dihydrogen phosphate
are
NHmuch
H
4 2 PO further
4 are away
used as from the central
fertilizers. They atom
are than
also they
used forare in
reprooNH 3ng
. Thus thepaper
wood, lone pair
and causes even
textiles. NH gr eater
4ClO 4 is
distortion
used as aninoxidizing
PH 3, A sHagent
3 and SbH
in .
solid
3 The
fuelbond
r angle
ocket decreases
propellants. to 91°18 (Table 10.17). These bond angles sug-
gest that in PH 3, A sH 3, SbH 3 and BiH 3 the orbitals used for bonding ar e close to pure p orbitals.
The melting
Phosphine PHand 3
boiling points of the hydrides increase from PH 3 through A sH 3 to SbH 3. The values
for NH 3 seem out of line with this trend: one might have expected the boiling point of NH 3 to be –110 °C or
Phosphine
–120 °C. ThePH 3 is a colourless
reason why NH 3 has andaextremely toxicpoint
higher boiling gas, which
and issmells
muchslightly of garlic
less volatile thanorexpected
bad sh. isI t that
is highly
it is
reactive. I t can be formed either by hydrolysing metal phosphides such
hydrogen bonded in the liquid state. The other hydrides do not form hydr ogen3 bonds. 3 2 as Na P or Ca P with water, or by
hydrolysing white phosphorus with NaOH solution.
These hydrides are strong reducing agents and react with solutions of metal ions to give phosphides,
arsenides and stibnides. They are ammable Ca3P2 + 6H and2O
extremely
2PH 3 +poisonous.
3Ca(OH ) 2
P4 + 3NaOH + 3H 2O PH 3 + 3NaH 2PO 2
Table 10.17 Some properties of the hydrides
PH 3, unlike NH 3, is not very soluble in water: aqueous solutions are neutral. I t is more soluble in CS2 and
m.p. Phosphonium
other organic solvents. b.p. salts such
Bond [PH 4] + Cl - can be formed,
asenergy Bond
but require PH
Bond angle
length
3 and anhydrous
–1
(°C) (°C) (kJ mol ) (Å)
H Cl (in contrast to the ready formation of NH 4X in aqueous solution). Pure PH 3 is stable in air, but it
catches
PH 3 −133.5
−34.5150 °C.
−77.8 to about
NH 3 re when heated
−87.5
N−H = 389
PHP–H
_
H −N –H = 107°48
= 318 H 3PO 4 H –P–H = 93°36
3 + 2O 2
1.017
1.419
@unacademyplusdiscounts
PH Afrequently
sH −116.3 traces−62.4
contains A s–H
of diphosphine PH= 247 H –itAto
which cause s–H = 91°48
catch 1.519 This is the
re spontaneously.
3 3 2 4
origin
SbHof3 the ickering
−88 light called
−18.4will-o’-the-wisp,
Sb–H = which
255 is sometimes
H –Sb–Hseen in marshes. 10.36
= 91°18 1.707 Hydrides 453

Some important chemical properties of phosphine ar e:

Donor propert
1. Some of theies
chemical properties of phosphine ar e similar to ammonia.
NH 3 cana.donate
Phosphine
its loneis weakly
pair ofbasic and lik
electrons e ammonia
quite stronglygives phosphonium
to form complexes.compounds
Thus ammonia with forms
acids. ammo-
+
nium NH 4 salts, and also coordination complexes PH 3 +with ® PHions
H Brmetal 4 Br
from the Co, Ni, Cu and Z n groups, for
example the [Co(NH 3) 6] 3+ ion, very readily.
PH 3b.acts
L ike
asNH 3, PH 3 can
an electron also form
donor addition
and forms compounds
numerous lik e, CuCl
complexes 2 × 2PH
such as [F3,3B × 2PH
A lCl 3PH 3, SnCl 4 × 2PH
3], [Cl 3A l PH 33]
Chapter 10.indd 452 and [Cr(CO)
c. Both3(PH
NH ) ]. A variety of other trivalent phosphorus
3 33 and PH 3 can be absorbed by bleaching powder . compounds such as PF 3, PCl 3, PEt 3 , P(OR) 3 3/21/2017 1
and PPh3 also form complexes, which in some ways resemble complexes with CO. Thus the lone pair on
P is used to form the coordinate PH 3 +bond 3Ca(OCl)Cl
to an empty+ 3H 2orbital
O ® PClon3 + 3HBClor+ 3
the Ca(OH
metal (a)s2 bond). In the case of
metals, this original coordinate NHbond 3 + 3Ca(OCl)Cl ® N 2 +by
may be reinforced 3Cback + 3H 2O from overlap of a lled d orbital
aCl 2 bonding
on the metal with an empty d orbital
2. Other chemical reactions are as follows: on P.
The donor properties of the other hydrides are very weak, and they have little or no tendency to form
PH 3 + O 2 150°C → H 3PO 4 + H 2O
a. bonds.
coordinate
In NH 3 the lone pair occupies an sp3 hybrid orbital. In A sH 3 and SbH 3 the bond angles become close
to 90° which 3 + 3Cl 2 that
b. PHsuggests → PCl the 3 + 3H Cl used for M—H bonding are almost pure p orbitals. If the three
orbitals
p orbitals are used for M—H bonding, the lone pair must occupy a spherical s orbital. This is larger, and
c. PH 3 and
less directional, + 4NO hence
2
electric
less → 4N 2 + for
spark effective
H 3 PO
forming
4 a coordinate bond. This means that any s bond will be
very weak. In addition the 4d and 5d orbitals are too large for effective back bonding. These two factors
accountd. forFormation
the difference of phosphides.
in complexing power between the hydrides.
Nitrogen forms several hydrides2PH + 3CuSO
(see 3Table 4 → Cu 3 P2 + 3H 2SO 4
10.18).
2PH
Table 10.18 Hydrides 3 + 3 H gCl → H g3P2 + 6H Cl
of 2nitrogen
Formula Name Oxidation state
e. PH 3 + 6A gNO 3 → [A g3P →3A gNO 3 ] → +3H NO 3
NH 3 yellow ppt. A mmonia –I I I
A g3 P →3A gNO 3 +2 34H 2O → 3A g → +3H NO 3 + H 3 PO 3 –I I
N H Hydrazine
NH 2OH black ppt.Hydroxylamine –I
f. PH 3 + 4H CH O + H Cl → [P(CH 2OH ) 4 ] + Cl →

Arsine AsH
Hydrazine N 23H, 4st ibine SbH 3 and bismut hine BiH 3
The bond
H ydrazine is aenergy (Table
covalent 10.17)
liquid, whichand the stability
fumes of smells
in air, and the hydrides
similar both
to NHdecrease on descending the group.
3. Pure hydrazine burns readily
Consequently,
in air arsine A
with the evolution ofsH 3, stibine
a lar ge amountSbH of3 and bismuthine BiH 3 are only obtained in small amounts. A sH 3
heat.
and SbH 3 are both very poisonous gases. A sH 3, SbH 3 and BiH 3 can be prepared by hydrolysing binary
metal compounds such N as2HZ4(l)
n3A+ sO,2(g) N 2(g) + 2H 2O H = − 621 kJ mol −1
2 M g3Sb2 or M g3Bi 2 with water or dilute acid. A sH 3 and SbH 3 are formed
in M arsh’s test for A s and Sb compounds..

St ruct ure of t he hydrides

Chapter 10.indd 454
The structure of ammonia may either be described as pyramidal, or tetrahedral with one position occupied3/21/2017 11

by a lone pair (Figure 10.29). This shape is predicted using the V SEPR theory since there are four electron
pairs in the outer shell. These comprise three bonding pairs and one lone pair. The repulsion between a
lone pair and a bond pair of electrons always exceeds that between two bond pairs. Thus the bond angles
are reduced from 109° 27¢ to 107° 48¢, and the regular tetrahedral shape is slightly distorted.

Electronic structure of 1s 2s 2p
 reduces I 2 and O 2.
N 2H 4 + 2I 2 _4H I + N 2
@unacademyplusdiscounts N 2H 4 + 2O 2 2H 2O 2 + N 2
N 2H 4 + 2CuSO 4 Cu + N 2 + 2H 2SO 4 10.36 Hydrides 455
I n acidic solutions, hydrazine usually behaves as a mild reducing agent, though powerful reducing agents
can
Thereduce
methyl N 2derivatives
H 4 to NH 3, thus
M eNHcausing N 2HM
NH 2 and 4 to be oxidized.
e2NNH 2 are mixed with N 2O 4 and used as a rocket fuel in the
space shuttle, in guided missiles, and (earlier) in the A pollo lunar modules.
II III
N 2H 4 is a weak base and reacts N 2with acids,
H 4 +Z forming two
n + 2HCl 2N series
H 3 + Zof salts. The salts are white ionic crystal-
nCl 2
line solids, and are soluble in water.
H ydrazine may act as an electron donor.NThe N atoms have a +lone pair of electrons, which can form coor-
2H 4 + H X N 2H 5+ X
dinate bonds to metal ions such as Ni 2+ and Co2+.
M ost of hydrazine produced is used N 2 Has4 + 2H X fuel.NI 2t His62+also
rocket +2Xused to treat the boiler feed water in
power
Whenstations
dissolvedtoinprevent oxidation
water (in of basic
neutral or the boiler and pipes.
solutions) hydrazine I n the
or laboratory
its salts arephenylhydrazine
powerful reducingisagents.
used
toThey
characterize
are used tocarbonyl
producecompounds and sugars
silver and copper by and
mirrors forming crystalline
to precipitate thederiv ativesmetals.
platinum calledHosazones.
ydrazine also
reduces I 2 and O 2.
CH 2 . OH N 2H 4 + 2I 2CH 24H. OHI + N2
| |
(CH .OH) 3 N 2H 4 + 2O 2(CH2H . OH)2O 2 + N 2
3
| |
N 2H 4 + 2CuSO 4 Cu + N 2 + 2H 2SO 4
CH . OH CH . OH
|
I n acidic solutions, hydrazine usually behaves as a mild | reducing agent, though powerful reducing agents
can reduce N 2H 4 to NH 3,CH O causing
thus + H 2 N NNH H
2 4
Cto6 H
be5 CH =
oxidized.N NH C 6 H 5 + H 2O
glucose phenylhydrazine glucose phenylhydr azone
II (an
I I I osazone)
N 2 H 4 +Z n + 2H Cl 2N H 3 + Z nCl 2
HHydrazine
ydrazineis
maystillactmanufactured
as an electronby the The
donor. Raschig process,
N atoms have in which
a lone pairammonia is oxidized
of electrons, which canbyform
sodium
coor-
hypochlorite in dilute aqueous solution.
2+
dinate bonds to metal ions such as Ni and Co . 2+

M ost of hydrazine produced

NHis3 +used as rocket
NaOCl NHfuel.
2Cl +I NaOH
t is also(fast)
used to treat the boiler feed water in
power stations to prevent oxidation of the boiler and pipes. I n the laboratory phenylhydrazine is used
2NH 3 + NH
to characterize carbonyl compounds and2Cl
sugarsNH
by2NH 2 + NH
forming 4Cl (slow) deriv atives called osazones.
crystalline
A side reaction between chloramine and hydrazine may destroy some or all of the pr oduct.
CH 2 . OH N H + 2NH Cl CHN2 .+ OH
2NH 4Cl
2 4 2
| | 2
This reaction is catalyzed(CH . OH ) 3metal ions present
by heavy (CH .
in OH )3
solution. For this reason distilled water is used
(rather than tap water), and| glue or gelatin is added to| mask (i.e. complex with) the remaining metal ions.
The use of excess of ammoniaCH . OH
reduces the incidenceCH
. OH
of chloramine reacting with hydrazine. The use of a
| |
dilute solution of the reactants is necessary to minimize
CH O + H N NH C H CH = N another side
NH Cr eaction:
H +H O
2 6 5 6 5 2
glucose phenylhydrazine
3NH 2Cl + 2NH 3glucose
N 2 + phenylhydr
3NH 4Cl azone
(an osazone)
The hydrazine is concentrated by distillation yielding N 2 H 4 àH 2O , or by adding H 2SO 4 to precipitate the
salt N 2 H 4 àH 2SO 4.
H ydrazine is still manufactured by the Raschig process, in which ammonia is oxidized by sodium
hypochlorite in dilute aqueous solution.
NH 3 + NaOCl NH 2Cl + NaOH (fast)

2NH 3 + NH 2Cl NH 2NH 2 + NH 4Cl (slow)

Chapter 10.indd 455

A side reaction between chloramine and hydrazine may destroy some or all of the pr oduct. 3/21/2017 11:27

N 2H 4 + 2NH 2Cl N 2 + 2NH 4Cl

This reaction is catalyzed by heavy metal ions present in solution. For this reason distilled water is used
(rather than tap water), and glue or gelatin is added to mask (i.e. complex with) the remaining metal ions.
The use of excess of ammonia reduces the incidence of chloramine reacting with hydrazine. The use of a
dilute solution of the reactants is necessary to minimize another side r eaction:
3NH 2Cl + 2NH 3 N 2 + 3NH 4Cl
The hydrazine is concentrated by distillation yielding N 2 H 4 àH 2O , or by adding H 2SO 4 to precipitate the
salt N 2 H 4 àH 2SO 4.

Chapter 10.indd 455 3/21/2017 11:

 458 Chapt er 10 The p-Block Elements and their Compounds
OGEN AZIDE AND THE AZIDES
(formerly called hydrazoic acid)
a pK a value of 5isina water
colourless
but isliquid
almostb.p.
completely is highly
ionized
_
The NH 3 removes H + and thus causes the reaction to proceed in the forward direction. Thus acetic acid has
37 °C, which in liquid ammonia. A mmonia thus reduces the
@unacademyplusdiscounts
n irritating odour. Both the liquid
difference and the
between the gas explode
str engths on heating
of acids. In this or with ammonia
respect a violent is called a levelling solvent.
10.40 NPK Fertilizers 461
2H N 3 | H 2 + 3N 2
10.38 HYDROGEN AZIDE AND THE AZIDES
stable in aqueous solution, Thebut widespread
should be use of nitrates
treated withas fertilizers
care. greatly boosts
It dissociates slightlycrop in yields. Since nitrates are soluble, the run-off
5). It behaves as aHweak water
ydrogen into
acid, azide lakes and
H N strength rivers also contains nitr ates. This causes several problems.
liquid b.p. 37 °C, which is highly
a of similar 3 (formerly calledacid.
to acetic hydrazoic
It reactsacid) is a colourless
with electro-
ng salts called azides,poisonous
but unlike and
other hasacid an +irritating
metal odour.
reactions, Both
no the
hydrogen
1. I t produces increased growth of algae and other aquatic plants, which may liquidis and
evolved.the gas explode on heating
clog upor withand
rivers a violent
lakes, and
shock. may make mudbanks in estuaries turn gr een.
6H N 3 + 4L i 4L iN 3 + 2NH 3 + 2N 2
lithium
2. There azide
is concern that nitrates are harmful 2H N 3 in H 2drinking
+ 3N 2 water. They cause a disease in babies called
methaemoglobinaemia,
H N 3explosives.
is slightly more stable inare which reduces the
aqueous solution, but should of amount beoxygen
treatedinwith baby’s
thecare. blood. I n extreme
I t dissociates slightly forms
in
used as detonators and this causes
Ionic the
azides
‘blue baby syndrome’ . There is also concern that nitrates could be linked with stomach
aqueous solution (pK 5). I t behaves as N a
3 weak acid, of similar strength to acetic acid. I t reacts with electro-
able, and some are used as organic intermediatesa andthe EEC have set a safety limit
positive cancer. Becausesalts
metals, forming of this,called azides, butC unlike N other N 3
acid of 25ppm
+ metal for nitr ates
reactions, in drinking
no hydrogen water.
is evolved.
C
method of making azides 3. is byThere
passingis some nitrousconcern oxide that denitri cation to oxides of nitrogen, particularly N 2O, may harm the ozone
6H N 3 + 4L i 4L iN 3 + 2NH 3 + 2N 2
layer.
de at 190 °C under anhydrous conditions. The water N lithium azide N
cts with more sodamide. A lternatively nitrous oxide
Covalent azides are used as detonators and C
explosives. I onic azides are
olution of sodamide in liquid ammonia as a solvent.
much |more
N3
10.40
usually NPK stable,FERTILIZERS
and some are used as organic intermediates and
N N3
N 2O + NaNH 2 NaN 3 + H 2O
dyestuffs. C C
N3
H 2O + NaNH 2 NHThe Plant
most fertilizers
importantnormally method contain of making thr ee mainisingredients:
azides by passing nitrous oxide
3 + NaOH
gas into fused sodamide at 190 °C under Figure anhydrous
10.31 as conditions.
Structure of The water
+ 2NaNH 2 NaN 3 + NH1. Nitrogen in a combined form
3 + N aOH
(commonly ammonium nitrate, other ammonium N salts Nor nitrates, or
vapour produced reacts with more sodamide. cyanuric A lternatively
triazide. nitrous oxide
obtained may be converted as urea).
to hydrogen Nitrogen is essential for plant growth,
azideofbysodamide in liquid ammonia as a solvent. particularly of leaves, since it is a constituent
C of amino
can be passed into a solution
acids and proteins, which must be made to make new cells.
4 followed by distillation. Lead azide Pb(N 3) 2 can be precipitated from a solution
a soluble lead salt such as 2.Pb(NO
Phosphorus 3) 2. Pb(N
N
for2O + NaNH
root growth,
3) 2 is sensitive 2 NaN
usually
to 3 +
shock asHaand
2O
slightly
is usedsoluble
as a form of phosphate such as ‘superphosphate’
N3
or ‘triple
high explosive charge. It is particularly reliable, superphosphate’
H 2O + NaNH and works . These
2
are made
even3 +inNaOH
NH from
damp conditions. phosphate rocks such as uoroapatite [3Ca3(PO 4) 2
CaF
al azides ar e known. Cyanuric triazide ] which
Nis2O a+ are
powerfulmined.
2NaNH explosive BasicNaN 3(Fslag, which
igure
+ NH is
10.31).a by-product from the steel industry,
Figure 10.31 Structureis also usedof as a
3 + N aOH
2
2
considered as a pseudohalide phosphate fertilizer.
ion. It forms the extremely unstable and explosive cyanuric triazide.
The sodium azide so obtained may be converted to hydrogen azide by
e FN 3 chlorazide ClN , bromazide
3.
treatment Potassium BrN
with H 2SO ,
ions and for iodazide
owering, I N , but
often the
provided dimer asNK —NSO . is
4 followed by distillation. L ead azide Pb(N 3) 2 can be precipitated from a solution
3 3 3 32 43

of sodium azide and a soluble lead salt such as Pb(NO 3) 2. Pb(N 3) 2 is sensitive to shock and is used as a
reduction with H 2S. detonator to set off a high explosive charge. I t is particularly reliable, and works even in damp conditions.
Urea
NaN 3 + H 2SNumerous
+ H 2O other
NH 3 +metal N2 + S azides
+ NaOH ar e known. Cyanuric triazide is a powerful explosive (Figure 10.31).
U rea(N
The is widely
) ¯
ion used
is as a nitrogenous
considered fertilizer. I ion.
as a pseudohalide t is very
I t formssoluble,
the and hence quick
extremely unstable acting,
andbut it is easily
explosive
N 3- ion
3
uter electrons and is isoelectronic
washed away.
compounds with
uorazideI t hasCO FN a2. very
The high
chlorazide is linear
nitrogen
ClN , (N—N—N)
content
bromazide (46%).
BrN ,Ias
t is manufactured
and iodazide I N , fromthe
but NH , andNthe
dimer —N reaction
3 3 3 3 3 3 3 is
al of two and two unknown. bonds,
proceeds givingin two N =stages.
N = N and s bond order of 2. Both N—N
ength, 1.16 Å . A nalysis of N 3- is by reduction with H 2S.
180- 200 C
de molecule has a bent structure. The addition 2NH 3 + CO of 2the ¾extra
¾¾¾¾¾ electron ® NH from H means D ® NH 2 × CO × NH 2 + H 2O
2COONH 4 ¾ ¾
t now occupy an antibonding MO, and hence the two N–N NaN +
high
3 bondH S +
pressure
2 H
lengths
2O NH
ammon 3 +i um
N 2 + S + NaOH urea
are different:
- carbonate
The N 3 ion has 16 outer electrons and is isoelectronic with CO 2. The N 3- ion is linear (N—N—N) as
is COI n112°
. There
2the soil,is ureaa total
slowly of hydrolyses
two and two to ammoniumbonds, giving N = N = N and s bond order of 2. Both N—N
carbonate.
bonds are the same length, 1.16 Å .
NH 2CONH 2 + 2H 2O (NH 4) 2CO 3
The hydrogen azide molecule has a bent structure. The addition of the extra electron from H means
N —N is 112°, and the two N —N bonds are of signi cantly different lengths, and the
that one electron must now occupy an antibonding M O, and hence the two N–N bond lengths are different:
ably 1.5 and 2 respectively. Phosphat e fert ilizers
112°
Phosphate rocks such as uoroapatite [3Ca3(PO 4) 2 CaF2] are very insoluble, and thus are of no use to plants.
Superphosphate is made by treating phosphate rock with concentrated H 2SO 4. The acid salt Ca(H 2PO 4) 2 is
more soluble, and over a period of weeks the superphosphate will dissolve in the soil water .
The bond angle H —N —N is 112°, and the two N —N bonds are of signi cantly different lengths, and the
bond orders are probably 1.5 and 2 respectively.
[ 3(Ca3 ( PO 4 ) 2 àCaF2 ] + 7H 2SO 4 3Ca (H 2PO 4 )2 + 7CaSO 4 + 2H F
superphosphat e

The CaSO 4 is an insoluble waste product, and is of no value to plants, but is not removed from the product
3/21/2017 11:27:40 AM
sold.

Chapter 10.indd 458 3/21/2017 11:2

Chapter 10.indd 461 3/21/2017

 __
@unacademyplusdiscounts
@unacademyplusdiscounts
462 Chapt er 10 The p-Block Elements and their Compounds
462 Chapt er 10 The p-Block Elements and their Compounds
‘Triple superphosphate’ is made in a similar way, using H 3PO 4 to avoid the formation of the waste product
‘Triple. superphosphate’ is made in a similar way, using H 3PO 4 to avoid the formation of the waste product
CaSO
CaSO4 4.
[3Ca3 (PO 4 ) 2 × CaF2 ] + 14H 3PO 4 ¾¾® 10Ca(H 2 PO 4 ) 2 + 2H F
[3Ca3 (PO 4 ) 2 × CaF2 ] + 14H 3PO 4 ¾¾® 10Ca(H 2 PO 4 ) 2 + 2HF
triple
triple
superphospaahte
superphospaahte
10.41 | |HALIDES
10.41 HALIDES
Trihalides
Trihalides
A ll the possible trihalides of N, P, A s, Sb and Bi are known. The nitrogen compounds are the least stable.
A ll theNF possible trihalides of N, P, A s, Sb and Bi are known. The nitrogen compounds are the least stable.
Though 3 is stable, NCl 3 is explosive. NBr 3 and NI 3 are known only as their unstable ammoniates NBr 3·
Though NF is stable,
6NH 3 and NI3 3· 6NH 3. The NCllatter
3 is explosive.
compound NBrcan3 andbeNImade3 are byknown only asI their
dissolving unstable ammoniates NBr 3·
2 in 0.880 NH 4OH . I t detonates
6NH and NI
unless3 excess ammonia 3· 6NH 3. The latter compound can be made
is present, and students are warned not to prepare by dissolving I 2 in 0.880 NH 4OH . ItThe
this compound. detonates
other
unless excess
16 trihalides are stable.ammonia is present, and students are warned not to prepare this compound. The other
16 trihalides are stable.
The trihalides are predominantly covalent and, like NH 3, have a tetrahedral structure with one position
occupied The by
trihalides
a lone pair. are predominantly
The exceptionscovalent are BiF3and,which likeisNH 3, have
ionic and athetetrahedral
other halides structure
of Bi with
and SbFone position
3 which
occupied by a lone
are intermediate in char acter. pair. The exceptions are BiF 3 which is ionic and the other halides of Bi and SbF3 which
areTheintermediate
trihalidesin character.
typically hydrolyse readily with water, but the products vary depending on the element:
The trihalides typically hydrolyse readily with water, but the products vary depending on the element:
NCl 3 + 4H 2O NH 4OH + 3H OCl
NCl 3 + 4H 2O NH 4OH + 3H OCl
PCl 3 + 3H 2O H 3PO 3 + 3H Cl
PCl 3 + 3H 2O H 3PO 3 + 3H Cl
A sCl 3 + 3H 2O H 3A sO 3 + 3H Cl
A sCl 3 + 3H 2O H 3A sO 3 + 3H Cl
SbCl 3 + H 2O SbO + + 3Cl - + 2H +
SbCl 3 + H 2O SbO + + 3Cl - + 2H +
BiCl 3 + H 2O BiO + + 3Cl - + 2H +
BiCl 3 + H 2O BiO + + 3Cl - + 2H +
They also react with NH 3. For example,
They also react with NH 3. For example,
PCl 3 + 6NH 3 P(NH 2) 3 + 3NH 4Cl
PCl + 6NH 3 P(NH 2) 3 + 3NH 4Cl
NF3 behaves differently from the others. I3t is unreactive, rather like CF4, and does not hydrolyse with water,
NF3 behaves
dilute acids or differently
alkali. I t does from the others.
react if sparkedIt iswith
unreactive, rather like CF4, and does not hydrolyse with water,
water vapour.
dilute
PF3acids or alkali.
is rather less Itreactive
does react if sparked
towards waterwithandwateris morevapour.easily handled than the other halides. The
PF3 isparticularly
trihalides, rather lessPF reactive
3, can towards
act as donor water and
molecules is more
using easily handled
their lone pair to than formthea other halides.
coordinate The
bond,
trihalides,
for exampleparticularly
in Ni(PF 3) 4PF . I n3,addition
can act as todonor
this s molecules
bond, there using
is their lone pairfrom
backbonding to forma lleda coordinate
orbital onbond,the
for example
metal to an empty in Ni(PF 3) 4. I n
d orbital onaddition
P, similartotothistheswaybond,COthereacts as isa ligand.
backbonding
Ni(PF3)from a lled orbital on the
4 can be made from nickel
metal toNi(CO)
carbonyl an empty 4. d orbital on P , similar to the way CO acts as a ligand. Ni(PF )
3 4 can be made from nickel
carbonyl Ni(CO) 4.
Ni(CO) 4 + 4PF3 Ni(PF3) 4 + 4CO
Ni(CO) 4 + 4PF3 Ni(PF3) 4 + 4CO
M any tri uorophosphine complexes of the transition metals are known. Though most of the trihalides are
Manyfrom
made tri uorophosphine
the elements, PF complexes
3 is made by of the transition
action of CaF metals
2 (orare known.
other Though
uoride) on most
PCl 3. of
PFthe trihalides
3 is a colourless,are
made from the elements,
odourless gas, which is very toxic PF 3 is made by the action of CaF (or other
because it forms a complex2 with haemoglobin in the blood,uoride) on PCl 3. PF is a colourless,
3 thus starving
odourless
the body ofgas, which is very toxic because it forms a complex with haemoglobin in the blood, thus starving
oxygen.
theNF body of little
3 has oxygen. tendency to act as a donor molecule. The molecule is tetrahedral with one position occu-
pied by NF3ahas
lone pair,
little and thetobond
tendency act as angle F—N—F
a donor molecule. is 102°30 . H owever,
The molecule the dipolewith
is tetrahedral moment is very occu-
one position low
(0.23
piedDby ebye units)
a lone compared
pair, and thewith bond 1.47D
angleforF—N—F
NH 3. Theis highly
102°30 electronegative
. H owever, the F atoms
dipoleattract
moment electrons,
is veryandlow
these
(0.23moments
D ebye units) partly cancel the
compared moment
with 1.47D from
for NH the3. The
lonehighly
pair, and this reduces both
electronegative F atoms the dipole
attract moment
electrons,andand
its donor
these power. partly cancel the moment from the lone pair, and this reduces both the dipole moment and
moments
The trihalides
its donor power. also show acceptor properties, and can accept an electron pair from another ion such as
F - , forming complex
The trihalides ions
also show suchacceptor 2-
as [ SbFproperties,
5] and [ Sband -
2 F7 ]can. They
accept also
anreact withpair
electron a variety of organometallic
from another ion such as
-
F , forming
reagents, formingcomplexcompoundsions such M Ras3. [ SbF5 ] and [ Sb2 F7 ] - . They also react with a variety of organometallic
2-

reagents, forming compounds MR 3.

Chapter 10.indd 462 3/21/2017 11:2

Chapter 10.indd 462 3/21/2017 11

 PCl 3 + Cl 2 (or S2Cl 2)
_
PCl 3 is the most important trihalide and some of it is used to mak e PCl 5.
PCl 5
@unacademyplusdiscounts
PCl 3 is widely used in organic chemistry to convert carboxylic acids to acid chlorides, and alcohols to alkyl
halides. 10.41 Halides 463
PCl 3 + 3RCOOH 3RCOCl + H 3PO 3
PCl 3 is the most important trihalide and some of it is used to mak e PCl 5.
PCl 3 + 3ROH 3RCl + H 3PO 3
PCl 3 + Cl 2 (or S2Cl 2) PCl 5
PCl 3 can be oxidized by O 2 or P4O 10 to give phosphorus oxochloride POCl 3.
PCl 3 is widely used in organic chemistry to convert carboxylic acids to acid chlorides, and alcohols to alkyl
halides. 2PCl 3 + O 2 2POCl 3
6PCl
PCl3 ++P3RCOOH
4O 10 + 6Cl 2 10POCl 3+ H PO
3RCOCl
3 3 3
POCl 3 is used in large amounts in the manufactur e of trialkyl
PCl 3 + 3ROH and+triaryl
3RCl H 3POphosphates (R O) 3PO.
3
OEt
PCl 3 can be oxidized by O 2 or P4O 10 to give phosphorus oxochloride POCl 3.
O PCl 3 + 3EtOH O P OEt Triethyl phosphate
2PCl 3 + O 2 2POCl 3
OEt
6PCl 3 + P4O 10 + 6Cl 2O . C10POCl
H . CH 36 4 3
Tritolyl
POCl 3 is used in
O large
PClamounts
3 + 3HO
inCthe
6H 4 manufactur
CH 3 Oe ofPtrialkyl and
O . C6H . triaryl
4 CH 3 phosphates (R O) 3PO.
phosphate
O . C6H 4 . CH 3
OEt
O 3 PCl + 3EtOH O P OEt Triethyl phosphate
Several of these phosphate derivatives are commercially important:
OEt
1. Triethyl phosphate is used in pr oducing systemic insecticides.
O . C6H 4 . CH 3
2. Tritolyl phosphate is a petr ol additive. Tritolyl
O PCl 3 + 3HO C6H 4 CH 3 O P O . C6H 4 . CH 3
3. Triaryl phosphates and trioctyl phosphate ar e used as plasticizers phosphate
for polyvinyl chloride.
O . C H . CH 6 4 3

PentSeveral of these phosphate derivatives are commercially important:

ahalides
Nitrogen1. Triethyl
is unablephosphate is used in pr oducing
to form pentahalides because systemic insecticides.
the second shell contains a maximum of eight electrons,
i.e. four2.bonds.
Tritolyl
Thephosphate is aelements
subsequent petr ol additive.
have suitable d orbitals, and form the following pentahalides:
3. Triaryl phosphates and trioctyl phosphate ar e used as plasticizers for polyvinyl chloride.
PF5 PCl5 PBr 5 PI 5
A sF5 (A sCl 5)
Pent ahalides SbF5 SbCl 5
BiF5
Nitrogen is unable to form pentahalides because the second shell contains a maximum of eight electrons,
i.e. four bonds. The subsequent elements have suitable d orbitals, and form the following pentahalides:
A sCl 5 is highly reactive and unstable, and has only a temporary existence. BiF5 is highly reactive,
and explodes with water, forming OPF 3 and
5 F2O. PCl
I t oxidizes
5 U FPBr
4 to
PI 5 BrF to BrF , and uorinates
5 U F6, and 3 5
A sF (A sCl
hydrocarbons. The pentahalides are prepared as follows:
5 5)
SbF5 SbCl 5
3PCl
BiF 5 5
+ 5A sF3 3PF5 + 5A sCl 3
PCl 3 + Cl 2 (in CCl 4) PCl 5
A sCl 5 is highly reactive and2A
unstable, and has
s2O 3 + 10F 4Aonly
sF5 +a3O
temporary existence. BiF5 is highly reactive,
2 2
and explodes with water, forming O 3 and F2O. I t oxidizes U F4 to U F6, and BrF3 to BrF5, and uorinates
hydrocarbons. The pentahalides are2Sbprepared
2O 3 + 10Fas 4SbF5 + 3O 2
2 follows:

2Bi ++ 5F
3PCl 5A2sF3 2BiF
3PF
5 5 + 5A sCl 3
5

These molecules have a trigonal bipyramid shape

PCl 3 +inClthe gas phase (see
PCl 5Figure 10.32), as expected from the
2 (in CCl 4)
V SEPR theory for ve pairs of electr ons.
2A s2O 3 + 10F2 4A sF5 + 3O 2
2Sb2O 3 + 10F2 4SbF5 + 3O 2
2Bi + 5F2 2BiF5
These molecules have a trigonal bipyramid shape in the gas phase (see Figure 10.32), as expected from the
V SEPR theory for ve pairs of electrons.

Chapter 10.indd 463 3/21/2017 11:27

Chapter 10.indd 463 3/21/201

 _
@unacademyplusdiscounts
464 Chapt er 10 The p-Block Elements and their Compounds

Cl

Cl
Cl
P

Cl

Cl

Figure 10.32 Structure of gaseous phosphorus pentachloride.

The valence bond explanation of the shape is:

Electronic structure of 3s 3p 3d
phosphorus atom –
ground state

Excited state

five singly filled orbitals form s bonds

to f ive atoms, giving a trigonal bi pyramid

The trigonal bipyramid is not a regular structure. Electron diffraction on PF5 gas shows that some
bond angles are 90° and others are 120°, and the axial P—F bond lengths are 1.58 Å whilst the equatorial
P—F lengths are 1.53 Å . I n contrast NM R studies suggest that all ve F atoms are equivalent. This paradox
may be explained quite simply. Electron diffraction gives an instantaneous picture of the molecule, whilst
NM R gives the picture averaged over several milliseconds. The axial and equatorial F atoms are thought
to interchange their positions in less time than that needed to take the NM R. The interchange of axial and
equatorial positions is called ‘pseudorotation’.
PF5 remains covalent and keeps this structure in the solid state. H owever, PCl 5 is close to the ionic–cova-
lent borderline, and it is covalent in the gas and liquid states, but is ionic in the solid state. PCl 5 solid exists as
[PCl 4] + and [ PCl 6 ] − : the ions have tetrahedral and octahedral structures respectively. I n the solid, PBr 5
exists as [PBr 4] + Br - , and PI 5 appears to be [PI 4] + and I - in solution.
PCl 5 is the most important pentahalide, and it is made by passing Cl 2 into a solution of PCl 3 in
CCl 4. World production is about 20 000 tonnes/year. Complete hydrolysis of the pentahalides yields the
appropriate -ic acid. Thus PCl 5 reacts violently with water:
PCl 5 + 4H 2O H 3PO 4 + 5H Cl
phosphoric
acid
I f equimolar amounts ar e used, the reaction is more gentle and yields phosphorus oxochloride POCl 3.
PCl 5 + H 2O POCl 3 + 2H Cl
PCl 5 is used in organic chemistry to convert carboxylic acids to acid chlorides, and alcohols to alkyl halides.
PCl 5 + 4RCOOH 4RCOCl + H 3PO 4 + H Cl
PCl 5 + 4ROH 4RCl + H 3PO 4 + H Cl
I t reacts with P4O 10, forming POCl 3, and with SO 2, forming thionyl chloride SOCl 2.
6PCl 5 + P4O 10 10POCl 3
PCl 5 + SO 2 POCl 3 + SOCl 2
PCl 5 also reacts with NH 4Cl, forming a variety of phosphonitrilic chloride polymers (see later).
nPCl 5 + nNH 4Cl (NPCl 2)n + 4nH Cl (ring compounds n = 3 to 8)
and
Cl 4P . (NPCl 2)n . NPCl 3 (chain compounds)

Chapter 10.indd 464 3

 10.42 Oxides of Nitrogen 465
Despite the existence of pentahalides, no hydrides MH 5 are known. To attain the ve-valent state, d orbitals
Despite thebe
must existence
used. Hof pentahalides,
ydrogen is not no
sufhydrides
ciently MH 5 are known.to
electronegative Tomake
attain the
the d ve-valent state, d orbitals
orbitals contract suf ciently,
must though
be used. H ydrogen is not suf ciently electronegative
PH F4 and PH 2F3 have been isolated. to make the d orbitals contract suf ciently,
though PH F4 and PH 2F3 have been isolated.

10.42 | OXIDES OF NITROGEN

10.42 | OXIDES OF NITROGEN
The oxides and oxoacids of nitrogen all exhibit p –p multiple bonding between the nitrogen and oxygen
The oxides
atoms.andThisoxoacids
does notofoccur
nitrogen
withallthe
exhibit p –p
heavier multiple
elements in bonding between
the group, the nitrogen nitrogen
and consequently and oxygen
forms a
atoms. This does not occur with the heavier elements in the group, and consequently nitrogen
number of compounds which have no P, A s, Sb or Bi analogues. Nitrogen forms a very wide range forms a
of oxides,
number of compounds which have no P , A s, Sb or Bi analogues. Nitrogen forms a very wide range of oxides,
exhibiting all the oxidation states from (+I ) to (+V I ). The lower oxides are neutral, and the higher ones are
exhibiting
acidicall the oxidation
(Table 10.19). states from (+I ) to (+V I ). The lower oxides are neutral, and the higher ones are
acidic (Table 10.19).
Table 10.19 Oxides of nitrogen
TableFormula
10.19 Oxides of nitrogen
Oxidation number Name
Formula Oxidation number Name
N 2O +I Nitrous oxide
N 2O +I Nitrous oxide
NO +I I Nitric oxide
NO +I I Nitric oxide
N 2O 3 +I I I Nitrogen sesquioxide
N 2O 3 +I I I Nitrogen sesquioxide
NO 2, N 2O 4 +I V Nitrogen dioxide, dinitrogen tetroxide
NO 2, N 2O 4 +I V Nitrogen dioxide, dinitrogen tetroxide
N 2O 5 +V D initrogen pentoxide
N 2O 5 +V D initrogen pentoxide
NO 3, N 2O 6 +V I Nitrogen trioxide, dinitrogen hexoxide
NO 3, N 2O 6 +V I Nitrogen trioxide, dinitrogen hexoxide
(very unstable)
(very unstable)

Nit rous oxide N O

Nit rous oxide N 2O 2
N 2O is a stable, relatively unreactive colourless gas. I t is prepared by careful thermal decomposition
N 2O of
is molten
a stable, relativelynitrate
ammonium unreactiveat about colourless
280 °C. I fgas. I t isstrongly
heated prepared by careful
it explodes. N 2Othermal
can alsodecomposition
be made by heating
of molten ammonium nitrate at about
a solution of NH 4NO 3 acidi ed with H Cl. 280 °C. If heated strongly it explodes. N 2O can also be made by heating
a solution of NH 4NO 3 acidi ed with H Cl.
NH 4NO 3 N 2O + 2H 2O
NH 4NO 3 N 2O + 2H 2O
N 2O is a neutral oxide and does not form hyponitrous acid H 2N 2O 2 with water nor hyponitrites with
Nalkali.
2O is a I t neutral
is importantoxideinand thedoes not formofhyponitrous
pr eparation sodium azide, acid andH 2hence
N 2O 2 with
also ofwater nor hyponitrites
the other azides: with
alkali. I t is important in the pr eparation of sodium azide, and hence also of the other azides:
N 2O + 2NaNH 2 NaN 3 + NH 3 + NaOH
N 2O + 2NaNH 2 NaN 3 + NH 3 + NaOH
The largest use of N 2O is as a propellant for whipped ice-cream. Because it has no taste, and is non-toxic, it
The largest
meets the use strict
of N 2O foodis as a propellant
and for whipped ice-cream. Because it has no taste, and is non-toxic, it
health r egulations.
meets theNstrict food and health r egulations.
2O is used as an anaesthetic, particularly by dentists. I t is sometimes called ‘laughing gas’, because
Nsmall
2O isamounts
used as an cause anaesthetic,
euphoria.particularly
I t requires aby dentists.
partial I t is of
pressure sometimes
760 mm Hcalledg of N‘laughing gas’, because
2O to anaesthetize a patient
smallcompletely.
amounts cause euphoria. I t requires a partial pressure of
Thus if dioxygen is also supplied, the patient may not be completely760 mm H g of N 2O to anaesthetize
unconscious. a patient
I f deprived
completely. Thus if dioxygen is also supplied, the patient may not be completely
of dioxygen for long, the patient will die. Plainly N 2O is unsuitable for long operations. U sually N 2O is unconscious. I f deprived
of dioxygen
administered for long, to putthethe
patient
patient will‘todie. Plainly
sleep’, and N O22Otois unsuitable
make for long
him recover operations. U sually N 2O is
consciousness.
administered to put the patient ‘to sleep’,
The molecule is linear as would be expected and O 2 to make him recover consciousness.
for a triatomic molecule with 16 outer shell electrons (see
The
also molecule
N -
and is linear
CO ). as would
However, CO be expected
is for a triatomic
symmetrical (O—C—O), molecule
whereas within16N 2outer
O theshell electrons
orbital energies (see
favour
- 3 2 2
also N
the and CO
3 formation 2). However, CO
of the asymmetrical 2 is symmetrical (O—C—O),
molecule N—N—O rather than the whereas in N O the orbital energies
2 symmetrical molecule N—O—N. favour
the formation
The bond of the asymmetrical
lengths the bondN—N—O
are short, andmolecule orders have rather
been than the symmetrical
calculated as N—N 2.73 molecule
and N—O N—O—N.
1.61.
The bond lengths are short, and the bond orders have been calculated as N—N 2.73 and N—O 1.61.
- + -
- +N N O N N
- O
N N O N N O

Nit ric oxide NO

Nit ric oxide NO
NO is a colourless gas and is an important intermediate in the manufacture of nitric acid by the catalytic
NO isoxidation
a colourless gas and is(Ostwald
of ammonia an important intermediate
process). in important
I t was also the manufacture
in the of nitric acid
obsolete by the catalytic
Birkeland–Eyde process
oxidation of ammonia (Ostwald process). I t was also important in the obsolete Birkeland–Eyde process

Chapter 10.indd 465 3/21/2017

Chapter 10.indd 465 3/21/2017 11:27:5
 2 +I
NO +II Nitric oxide
N 2O 3 +III Nitrogen sesquioxide
NO 2, N 2O 4 +IV Nitrogen dioxide, dinitrogen tetroxide
N 2O 5 +V Dinitrogen pentoxide
NO 3, N 2O 6 +VI Nitrogen trioxide, dinitrogen hexoxide
(very unstable)

Nit rous oxide N 2O

N 2O is a stable, relatively unreactive colourless gas. It is prepared by careful thermal decomposition
of molten ammonium nitrate at about 280 °C. If heated strongly it explodes. N 2O can also be made by heating
a solution of NH 4NO 3 acidi ed with H Cl.
NH 4NO 3 N 2O + 2H 2O
N 2O is a neutral oxide and does not form hyponitrous acid H 2N 2O 2 with water nor hyponitrites with
alkali. It is important in the pr eparation of sodium azide, and hence also of the other azides:
N 2O + 2NaNH 2 NaN 3 + NH 3 + NaOH
The largest use of N 2O is as a propellant for whipped ice-cream. Because it has no taste, and is non-toxic, it
meets the strict food and health r egulations.
N 2O is used as an anaesthetic, particularly by dentists. It is sometimes called ‘laughing gas’, because
small amounts cause euphoria. It requires a partial pressure of 760 mm H g of N 2O to anaesthetize a patient
completely. Thus if dioxygen is also supplied, the patient may not be completely unconscious. If deprived
of dioxygen for long, the patient will die. Plainly N 2O is unsuitable for long operations. U sually N 2O is
administered to put the patient ‘to sleep’, and O 2 to make him recover consciousness.
The molecule is linear as would be expected for a triatomic molecule with 16 outer shell electrons (see
also N 3- and CO 2). However, CO 2 is symmetrical (O—C—O), whereas in N 2O the orbital energies favour
the formation of the asymmetrical molecule N—N—O rather than the symmetrical molecule N—O—N.
The bond lengths are short, and the bond orders have been calculated as N—N 2.73 and N—O 1.61.
- + -
N N O N N O

Nit ric oxide NO

NO is a colourless gas and is an important intermediate in the manufacture of nitric acid by the catalytic
oxidation of ammonia (Ostwald process). It was also important in the obsolete Birkeland–Eyde process

Chapter 10.indd 465 3/21/2017

@unacademyplusdiscounts _
@unacademyplusdiscounts
466 Chapt er 10 The p-Block Elements and their Compounds
466 Chapt er 10 The p-Block Elements and their Compounds
which involved sparking dinitrogen and dioxygen. NO is prepared in the laboratory by the reduction
-
ofwhich
diluteinvolved
H NO 3 with Cu, or dinitrogen
sparking reduction of H NO
and 2 with I NO
dioxygen. : is prepared in the laboratory by the reduction
-
of dilute H NO 3 with Cu, or reduction of H NO with I
3Cu + 8H NO 2 2NO + 3Cu(NO : ) + 4H O
3 3 2 2
3Cu
2H NO + 8H+NO 2I -3 + 2H2NO+ +2NO
3Cu(NO + I2 +3) 22H
+ 4H 2O
2 2O
- +
NO is a neutral oxide and is not an2H NOanhydride.
acid 2 + 2I + 2H 2NO + I 2 + 2H 2O
NONO is ahas 11 valency
neutral oxide andelectrons.
is not Ian
t isacid
impossible
anhydride. for them all to be paired, and hence this is an odd electron
molecule NO has and11 the gas is paramagnetic.
valency I t is diamagnetic
electrons. I t is impossible for them in the liquid
all to and solid
be paired, andstates,
hencebecause
this is anthe oddmolecule
electron
dimerizes
moleculeforming and the O—N—N—O.
gas is paramagnetic. The asymmetrical
I t is diamagnetic dimer in O—N—O—N
the liquid and solid has been
states,observed
becauseto thebemolecule
formed
as a red solid
dimerizes in the O—N—N—O.
forming presence of H Cl The or asymmetrical
other L ewis acids. dimer O—N—O—N has been observed to be formed
as aTheredbond
solid length N—O is of
in the presence HÅ
1.15 Cl, or
which otheris L intermediate
ewis acids. between a double and a triple bond. Bonding
is bestThe described
bond length usingN—O is 1.15 Å ,orbital
the molecular which is theory (see Chapter
intermediate between 3). The bonding
a double and is a similar to that
triple bond. in N 2
Bonding
and CO described
is best which both have
using the10molecular
outer electrons. orbitalNO has (see
theory 11 outer electrons,
Chapter 3). Theand the extra
bonding unpaired
is similar electron
to that in N 2
occupies
and CO an antibonding
which both have*2p 10 orbital. This reduces
outer electrons. NO thehasbond11 outerorderelectrons,
from 3 inand the2 21extra
N 2 to in NO. I f this electron
unpaired electron
isoccupies
removedanbyantibonding
oxidizing NO, *2ptheorbital.
nitrosonium ion NOthe
This reduces
+
isbond
formed. NO + the
I n from
order 3 inbond
N 2 toorder
2 21 in is
NO.3, and N—O
theelectron
I f this
theÅnitrosonium
in NO to 1.06 ionÅNOin NO +
bond length by
is removed contracts
oxidizing fromNO, 1.15 +
.
is formed. I n NO the bond order is 3, and the N—O
+

bond Odd electron

length molecules
contracts from are Å in NO
1.15usually to 1.06
highly Å in NO
reactive and+.tend to dimerize, NO is unusually stable for an
odd electron
Odd electron molecule. Nevertheless
molecules are usuallyit reacts
highly instantly
reactivewith anddioxygen to give NO
tend to dimerize, NO2, and with thestable
is unusually halogens it
for an
gives nitrosyl halides,
odd electron molecule. e.g.Nevertheless
NOCl. it reacts instantly with dioxygen to give NO 2, and with the halogens it
gives nitrosyl halides, e.g. NOCl.
2NO + O 2 2NO 2
2NO + O 2NO
2NO + Cl 2 2 2NOCl2
2NO + Cl 2 2NOCl
NO readily forms coordination complexes with transition metal ions. These complexes are called nitro-
syls. Fe 2+
and NOforms
NO readily formcoordination
the complexcomplexes [Fe(H 2O) 5with NO] 2+ , which ismetal
transition responsible
ions. Thesefor complexes
the colour are in the ‘brown-
called nitro-
syls.test’
ring Fe2+ for
andnitrates.
NO form M ost
the nitrosyl
complexcomplexes[Fe(H 2O) 5are 2+
NO]coloured.
, which is A nother
responsible example
for theis sodium
colour in the ‘brown-
nitroprusside
Na test’ for . 2H O.
2[Fe(CN)
ring 5NO]nitrates. 2 M ost nitrosyl complexes are coloured. A nother example is sodium nitroprusside
Na2NO often5NO]
[Fe(CN) . 2H
acts as a 2three-electron
O. donor, in contrast to most ligands which donate two electrons. Thus
threeNO CO often
groups may
acts asbe replaced by two
a three-electron NO groups:
donor, in contrast to most ligands which donate two electrons. Thus
three CO groups may be replaced by two NO groups:
[Fe(CO) 5] + 2NO [Fe(CO) 2(NO) 2] + 3CO
[Fe(CO) 5] + 2NO [Fe(CO) 2(NO) 2] + 3CO
[Cr(CO) 6] + 4NO [Cr(NO) 4] + 6CO
[Cr(CO) 6] + 4NO [Cr(NO) 4] + 6CO
I n these complexes the M —N—O atoms are linear, or close to linear. H owever, in 1968 the M —N—O
angleI ninthese[I r(CO)(Cl)(PPh
complexes the 3 M
)(NO)]—N—O +
was found
atoms to
are be 123°,
linear, or and
close since
to then Haowever,
linear. numberinof1968 other M —N—O
thecomplexes
have
angle been
in [Ifound with bond angles
r(CO)(Cl)(PPh 3)(NO)] in +
the
was range
found 120—130°.
to be These
123°, and bent
since bonds,
then which
a are
number weaker
of other than straight
complexes
bonds,
have been are offound
considerable
with bond theoretical
angles in the interest.
rangeNO 120—130°.
may also act as
These benta bridging ligandare
bonds, which between
weakertwo thanorstraight
three
metal
bonds, atoms
are ofinconsiderable
a similar waytheoretical
to CO. interest. NO may also act as a bridging ligand between two or three
metal atoms in a similar way to CO.
Nit rogen sesquioxide N 2O 3
Nit rogen sesquioxide N 2Otemperatures.
N O can only be obtained at low 3 I t can be made by condensing equimolar amounts of NO
2 3
and
N 2ONO 2 together,
3 can or by reacting
only be obtained at lowNO with the appropriate
temperatures. amount
I t can be made by of O 2. This gives
condensing a blue amounts
equimolar liquid or of
solid,
NO
which
and NO is unstable
2 and
together, ordissociates
by reactinginto
NO NOwithand
theNO at –30
appropriate
2 °C.
amount of O 2 . This gives a blue liquid or solid,
which is unstable and dissociates into NO and NO 2 at –30 °C.
NO + NO 2 N 2O 3
NO + NO NO
4NO + O 2 2 2N 22O 33
4NO + O 2 2N 2O 3
I t is an acidic oxide and is the anhydride of nitr ous acid H NO 2. With alkali it forms nitrites.
I t is an acidic oxide and is the anhydride of nitr ous acid H NO 2. With alkali it forms nitrites.
N 2O 3 + H 2O 2H NO 2
N 2O 3 + H 2O 2H NO
N 2O 3 + NaOH 2NaNO 2 + 2H 2O
N 2O 3 + NaOH 2NaNO 2 + H 2O
N 2O 3 reacts with the concentrated acids, forming nitrosyl salts:
N 2O 3 reacts with the concentrated acids, forming nitrosyl salts:
N 2O 3 + 2H ClO 4 2NO[ClO 4] + H 2O
N 2O 3 + 2H ClO 4 2NO[ClO 4] + H 2O
N 2O 3 + 2H 2SO 4 2NO[H SO 4] + H 2O
N 2O 3 + 2H 2SO 4 2NO[H SO 4] + H 2O

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10.42 Oxides of Nitrogen 467

The oxide exists in two different forms (Figure 10.33). These may be interconverted by irradiation with
light of the appropriate wavelength. The N—N bond length from microwave spectra is 1.864 Å in the
asymmetrical form. This is exceptionally long and thus the bond is exceptionally weak compared with the
N—N bond found in hydrazine (length of 1.45 Å ). Solid N 2O 3 exists in the form [N O] + [NO 2] −.

O O
O N N O
N N
O
Symmetrical form colation O
(has a two fold axis) Asymmetrical form
(colourless) (blue)
(a) (b)

Figure 10.33 Two forms of N 2O 3.

Nit rogen dioxide NO 2 and dinit r ogen t et roxide N 2O 4

NO 2 is a red–brown poisonous gas and is produced on a large scale by oxidizing NO in the Ostwald process
for the manufacture of nitric acid. I n the laboratory it is prepared by heating lead nitrate:
2Pb(NO 3) 2 2PbO + 4NO 2 + O 2
The gaseous products O 2 and NO 2 are passed through a U -tube cooled in ice. The NO 2 (b.p. 21°C) con-
denses. The Pb(NO 3) 2 must be carefully dried, since NO 2 reacts with water. The NO 2 is obtained as a brown
liquid which turns paler on cooling, and eventually becomes a colourless solid. This is because NO 2 dimer-
izes into colourless N 2O 4. NO 2 is an odd electron molecule, and is paramagnetic and very reactive. I t dimer-
izes to N 2O 4, pairing the previously unpaired electrons. N 2O 4 has no unpaired electrons and is diamagnetic.

2NO 2 N 2O 4
paramagnetic diamagnetic
( brown) ( colourless)
N 2O 4 is a mixed anhydride, because it reacts with water to give a mixtur e of nitric and nitrous acids:
N 2O 4 + H 2O H NO 3 + H NO 2
The H NO 2 formed decomposes to give NO.
2H NO 2 NO 2 + NO + H 2O
2NO 2 + H 2O H NO 3 + H NO 2
Thus moist NO 2 or N 2O 4 gases are strongly acidic.
The NO 2 molecule is angular with an O—N—O angle of 132°. The bond length O—N of 1.20 Å is
intermediate between a single and a double bond. X -ray diffraction on solid N 2O 4 shows the structure to
be planar.
O O
1.64 A°
N N

O O

The N—N bond is very long (1.64 Å ), and is therefore weak. I t is much longer than the single bond
N–N distance of 1.47 Å in N 2H 4, but there is no satisfactory explanation of why it is long.
L iquid N 2O 4 is useful as a non-aqueous solvent. I t self-ionizes:
N 2O 4 NO + + NO -3
acid base

The NO 2–N 2O 4 system is a strong oxidizing agent. NO 2 reacts with uorine and chlorine, forming nitryl
uoride NO 2F and nitryl chloride NO 2Cl. I t oxidizes H Cl to Cl 2 and CO to CO 2.

Chapter 10.indd 467 3/21/2017